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Dipartimento di Ingegneria dell'Impresa, Universit degli Studi di Roma Tor Vergata, Via del Politecnico, 1-00133 Roma, Italy
Dipartimento di Ingegneria Meccanica ed Aerospaziale, Sapienza Universit degli Studi di Roma, Via Eudossiana, 18-00184 Roma, Italy
a r t i c l e
i n f o
Article history:
Received 3 August 2013
Accepted in revised form 23 September 2013
Available online 2 October 2013
Keywords:
Adhesion
Scratch resistance
Damage mechanisms
Siliconeepoxy
Coatings
a b s t r a c t
Organicinorganic hybrid coatings have achieved success in scientic environments because they can be
designed using the solgel route to combine the high hardness and chemical stability typical of glass-like or
ceramic materials (i.e., the inorganic side) with the toughness and ductility typical of organic materials
(i.e., the organic side). Nevertheless, organicinorganic hybrid coatings are often very brittle, and they can
collapse if applied as thick lm on rigid substrates because of the shrinkage during the drying/curing process.
However, the manufacturing of a thick coating is compulsory, when stringent requirements for scratch performance and wear endurance must be met. In this respect, the present investigation proposes the design of selfdrying siliconeepoxy resins and the manufacturing of the corresponding thick coatings (approximately
~120 m thick) on as-received and micro-corrugated glass using an automatic drawdown applicator. The scratch
performance of the coatings was tested using progressive- and constant-mode scratch tests, and the wear
resistance was examined using dry sliding linear reciprocating tribological tests. The experimental ndings
demonstrate how the role of the interface is crucial and how micro-corrugation is extremely benecial in increasing the threshold of the maximum thickness beyond that at which coating bulging and delamination occur.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Organicinorganic hybrid coatings have achieved success in scientic
environments because they can be designed via solgel route to
combine the high hardness and chemical stability typical of glass-like
or ceramic materials (i.e., the inorganic side) with the toughness and
ductility typical of organic materials (i.e., the organic side) [1,2]. These
coatings could be protably used in several domains where substrate
protection and/or functionalization by a tailor-made coating material
are pursued [3]. In addition, the potential of these coatings is greatly
emphasized because they offer good adhesion to various substrates [3].
Furthermore, some of these coatings can dry/cure at relatively moderate
temperature (i.e., ~70250 C [4]), making them suitable as topcoats for
a large share of substrates, including some thermolable substrates. Nevertheless, organicinorganic hybrid coatings are often very brittle [57]
and they can collapse if applied as thick lm on rigid substrates due to
shrinkage during the drying/curing process [8,9]. Malzbender and de
With observed that the shrinkage phenomenon related to the drying/
curing process of organicinorganic hybrid coatings can often induce a
large residual stress eld inside the coating material, which can lead to
an early failure of the coating if applied with a thickness over intrinsic
critical values [9]. In particular, when the organicinorganic hybrid coatings are deposited on non-compliant substrates such as glass substrates,
the mismatch at the interface between the shrunk coatings and underlying substrates is strongly emphasized and this mismatch can increase
the possibility of a spontaneous collapse of the coating system, which
can bulge or even delaminate from the substrate even without the application of an external load.
Thus, preventing the bulging and delamination phenomena of
organicinorganic hybrid coatings synthesized via the solgel route is
of utmost interest as it would greatly extend applications of this class
of materials. In this respect, many efforts have been made by scientists
and practitioners to widen the range of coatings that could be designed
and manufactured via the solgel route. However, the proposed
solutions converged toward the implementation of very thin coatings
(i.e., typically a few microns) to reduce the onset of the detrimental
stress eld by material shrinking and toward the adhesion being mainly
improved through the combination of two or more organicinorganic
molecules, some with only mere grafting functionality. Such thin coatings have been used in industrial applications such as for optical, decorative or architectural materials. For example, the large-scale dip coating
process to prepare reective and antireective layers based on Pd
containing TiO2 or SiO2/TiO2 systems has become a well-established
technology (Irox, Amiran, Calorex, Schott Co.) [10]. Similarly, antireective coatings suitable as cover sheets for photovoltaic (PV) cells
and collectors have been commercially available from nearly a decade,
although their preparation involves a relatively high temperature
213
Fig. 1. 3D maps of the as-received and coated glasses: (a) as-received glass, (b) sandblasted glass, (c) as-received coated glass, and (d) sandblasted coated glass.
214
pattern. The sliding speed of the scratch indenter was varied from 0.2 to
100 mm/min.
Progressive load scratch tests were performed with the same
indenters (200 and 800 m tip radii). The applied load, along the
3 mm pattern, was progressively increased from 0 to 30 N for the indenters with the 800 and 200 m tip radii. The sliding speed was kept
constant at 1 mm/min.
The scratch equipment enabled the measurement of the normal and
tangential forces and of the penetration and residual depths, that is, the
penetration of the indenter tip inside the coating material during the
application of the load and after the load release and recovery in the
elastic eld of the indented material. For this purpose, the initial prole
on which the scratch test was to be performed was measured by probing it at a constant applied load of 0.03 N during the pre-scan and, then,
subtracting the indenter position during the application of the load
(scan), thus determining the penetration depths. The residual depths
were measured during the post-scan by applying the minimal load of
0.03 N and probing the scratched surface again after the recovery of
the material in the elastic eld. The analysis of the scratch pattern
after the load release was also performed using a eld emission gunscanning electron microscopy (FEG-SEM Leo, Supra35, Carl Zeiss SMT,
Inc. Thornwood, NY, USA) and stereomicroscopy (SMZ 745T, Nikon,
Japan).
The wear resistance of the siliconeepoxy coatings was investigated
by performing dry sliding linear reciprocating tribological tests
(Tribometer, C.S.M. Instruments, Peseaux, Switzerland), using a spherical antagonist (6 mm in diameter, 100Cr6 bearing steel). Incremental
sliding distances of up to 500 m were considered. The load during the
tribological tests was set at 1 N, the sliding frequency was set at 3 Hz
and the sliding distance for each stroke was set at 6 mm. The equipment
permitted the measurement of the friction during the test. In addition,
after the load release and recovery of the material in the elastic eld,
the wear pattern was monitored by contact gauge prolometry, SEM
and stereomicroscopy. The prolometry allowed for the 3D rebuilding
of the wear pattern (resolution of 2 m) and thus the estimation of
the amount of abraded material during the tribological tests.
215
Fig. 3. SEM images of to the residual scratch pattern after constant mode scratch tests. The measurement conditions were: an indenter with an 800 m tip radius and a normal load of 20 N.
The test was performed on the as-received substrates (ae) and sandblasted substrates (fl). The sliding speeds were: (a, f) 0.2 mm/min, (b, g) 1 mm/min (c, h) 5 mm/min, (d, i) 25 mm/min,
and (e, l) 100 mm/min.
216
Fig. 4. Trends in the friction force during constant-mode scratch testing. The test was
performed using an indenter with an 800 m tip radius at an applied load of 20 N.
signicantly decreasing the reaction grade. However, thermal crosslinking is impractical when it should be performed on in-service glass
panels. At ambient temperature, although the reagents (i.e., the epoxy
groups on the silicone skeleton and the amine groups on the hardeners)
have considerable time to combine, their motility is limited by the
intrinsic viscosity of the formulation. The viscosity can be regulated by
the solvent concentration. However, the viscosity of the mixture increases rapidly once cross-linking begins. The corresponding motility
of the molecule inside the mixture is largely reduced and gelation
can occur rather quickly, thus limiting the maximum degree of crosslinking and the maximum coating hardness achievable.
In the present investigation, the coating thickness was always
maintained at ~120 m, which is at least one order of magnitude greater
than the thickness selected for the application of common coatings on
glass manufactured via the solgel route [4,20,21]. The deposition of
such a thick coating on an already in-service stiff glass substrate at ambient temperature is troublesome. In fact, it involves a massive shrinkage
of the resin during the simultaneous drying/cross-linking process with
a non-compliant substrate. Thus, shrinkage is one source for the onset
of a major stress eld that is retained inside the coating. The stress is
tensile, acting parallel to the coatingsubstrate interface, and may be sufciently high to lead to spontaneous breakage and delamination at the
interface of the coating from the underlying substrate as shown in
Fig. 2a and reported in the literature [8,9]. Such a stress eld cannot be
relieved when the coating is deposited on a non-compliant substrate
such as stiff glass. However, a proper design of the coatingsubstrate
interface can oppose the action of the stress eld. In particular, this opposition can be performed by increasing the interfacial contact surface
between the coating and substrate by corrugation. Corrugation creates
interruptions on the very smooth glass surface in the form of microasperities. The widespread presence of micro-asperities that are well
distributed on the coating surface acts as an obstacle against the action
of the stress eld generated by the shrinkage phenomenon of the resin
on the stiff glass during the drying/cross-linking process. Thus, such
micro-asperities mechanically oppose the spread of the stress eld,
potentially preventing early failure of the coating (Fig. 2b).
The implementation of the latter step includes the selection
between two methods of increasing the interfacial adhesion on in
service glass: (i) chemical etching of the glass substrate with aggressive (acidic) solutions to promote micro-coarsening of the surface;
and (ii) sandblasting of the glass surface with ne glass-beads to
achieve micro-coarsening due to the impingements of the beads on
the brittle substrate. The former route is substantially impractical
217
Fig. 5. Penetration and residual depths of: (a, c) as-received substrates, (b, d) sandblasted substrates. The test was a constant-mode scratch test using an indenter with an 800 m tip radius
at an applied load of 20 N.
However, the tangential forces enables the indenter tip to move along
the scratch pattern with the nal purpose of maintaining the normal
applied load at the set value of 20 N. Thus, the coating material opposes
resistance to the advancing indenter. The resistance that the indenter is
able to oppose depends largely on the intrinsic features of the material
and the mechanism by which the material deforms during the application of the scratch load. As stated above, the indenter presses the
material ahead of its advancing tip, generating a compressive stress
eld inside the coating and its local plastic deformation. This phenomenon leads to the accumulation of some coating material in the form of a
plastic pile-up in front of the advancing indenter. It could be speculated
that the micro-roughened interface is better able to withstand the
Fig. 6. SEM images of the residual scratch patterns after progressive-mode scratch test. The measurement conditions were: an indenter with an 800 m tip radius, an incremental normal
load of 030 N and a sliding speed of 1 mm/min. The test was performed on the (a) as-received substrate and (b) sandblasted substrate.
218
the coating and substrate [15], with the substrate corrugation often
playing a fundamental role for different systems (for instance, epoxy
on sandblasted carbon laminates [26]).
The SEM images in Fig. 3 also reveal that both the number and size of
the transversal cracks are recorded when varying the sliding speed. In
particular, at the higher sliding speeds of 25 and 100 mm/min, no significant crack damage is visible either on the deposited coatings or asreceived glass. The sensitivity of the coating material to the sliding
speed is likely ascribed to the organic moieties of the resin. The organic
materials are extremely sensitive to the speed at which a load is applied,
that is, to the load rate [27]. Polymeric materials can exhibit a stiffer
response as the load rate is increased [28]. The stiffer deformation
response is typically ascribed to the time-dependent response of the
macromolecules, which have an intrinsic time to respond to an external
load and deform accordingly [29]. When the loading rate is excessive,
the macromolecules that the organic material is composed of have a
very short time to comply with the load and behave stify. In contrast,
when the loading rate is low, the macromolecules have more time to
comply with the load, thus deforming signicantly and behaving with
more compliance. In this case, the contribution of the organic moieties
of the resin cannot be neglected. Thus, when the coating material is
subjected to an increasing load rate, the organic moieties of the resin
behaves stify because of their intrinsic visco-elasticity and the coating
system is better able to withstand the action of the sliding indenter,
with no visible cracks appearing along the scratch pattern, regardless
of the geometrical features of the interface between the coating and
substrate surface.
Fig. 5 presents the trend of the penetration and residual depth
measured on the siliconeepoxy coatings deposited on both the asreceived (panel 2ac) and sandblasted glass (panel 2bd) after
constant-mode scratch tests at a load of 20 N and variable sliding
speed (0.2100 mm/min) against an indenter with a tip radius of
800 m. The extent of deformation under the application of the load is
similar for all coatings regardless of whether they were deposited on
as-received or sandblasted glasses, with an average penetration depth
of ~30 m. In addition, the aforementioned sensitivity of the coating
material to the imposed sliding speed is conrmed, as the penetration
depth increases by several microns when the sliding speed is decreased.
Because the residual depth is nearly negligible for all investigated scenarios (always less than 3.5 m), the deformation response of the coating can be considered visco-elastic. The coatings are considered viscous
because they are sensitive to the imposed sliding speed during the
219
Fig. 8. SEM images of the residual scratch patterns after constant-mode scratch tests. The measurement conditions were: an indenter with a 200 m tip radius and a normal load of 17 N.
The test was performed on as-received substrates (ae) and sandblasted substrates (fl). The sliding speeds were: (a, f) 0.2 mm/min, (b, g) 1 mm/min (c, h) 5 mm/min, (d, i) 25 mm/min
(e, l) 100 mm/min.
beginning of the scratch pattern, within the rst 0.5 mm. This result is
demonstrated by the sudden jump of the penetration and residual
depths to values near the average coating thickness (Fig. 9a and c).
The observed failure mechanism can fall within the mechanism of buckling and brittle spallation, which is consistent with [22]. As stated previously, the coating material is subjected to a load that is greater than its
critical load or, otherwise, greater than its adhesive strength to the
underlying substrate. Thus, a brittle fracture is generated at the interface
between the coating and substrate. The fracture propagates rapidly and
causes the delamination of the coating on a very large area. The SEM
images in Fig. 8ae only allow the delamination of the material to be
discerned. No differences were observed with varying sliding speeds;
furthermore, the fastest load rate causes the complete failure of the
220
Fig. 9. Penetration and residual depth: (ac) as-received substrates, and (bd) sandblasted substrates. The test was performed in constant mode using an indenter with a 200 m tip radius
and an applied load of 20 N.
and is completely torn off from the underlying substrate, thus generating an extended delamination zone, that is smaller than the bulged
zone. The coatings deposited on the sandblasted substrates exhibited
a clearly improved scratch response. Although several and repeated
cracks can be observed on the coating surface in Fig. 8fl, there is no
delamination and the coating damage is conned well within the actual
contact area between the scratch indenter and surface. In Fig. 10b (sliding speed of 1 mm/min), the coating is not characterized by any bulging
phenomenon and remains rmly adhered to the underlying substrate
despite the onset of fairly severe cracks. The failure mechanisms of the
coatings deposited on the sandblasted substrates are signicantly
affected by the sliding speed (Fig. 8fl). The damage on the coating
surface is larger at the lowest sliding speed (0.2 and 1 mm/min). The
damage consists of the superimposition of two failure mechanisms:
(i) the aforementioned C-shaped cracks, which imply the presence of
the brittle tensile cracking mechanism; and (ii) linear cracks (i.e., layer
break [20]) that develop along the axis of the scratch pattern related
to a presumable cutting of the coating material by the sharp indenter
tip. The latter mechanism is compatible with the nature of the glass substrate, which is extremely rigid and not compliant when submitted to
an external load. In the present case, as the overlying siliconeepoxy
coatings lay on the undeformable glass substrate, they can also be cut
off along the sliding direction of the indenter when indented with a
sharp tip, beyond being fractured according to the tensile cracking
Fig. 10. Optical microscope images of the residual scratch pattern after constant mode scratch test. The measurement conditions were: an indenter with a 200 m tip radius, a normal load
of 20 N and a sliding speed of 1 mm/min. Samples: (a) coating on an as-received substrate and (b) coating on a sandblasted substrate.
221
Fig. 11. SEM images of the residual scratch pattern after progressive-mode scratch test performed on a) an as-received substrate and b) a sandblasted substrate. The measurement
conditions were: an indenter with a 200 m tip radius, an incremental load from 0 to 30 N and a sliding speed of 1 mm/min.
Table 1
Denition of the critical loads of the siliconeepoxy coatings on the as-received and
sandblasted glass substrates after scratch tests using an indenter with a 200 m tip radius.
Critical loads/progressive, 200 m
Coatings on the
sandblasted glass
Coatings on the
as-received glass
Not applicable
~2 N
~13 N
Not applicable
~16 N
Not applicable
~7 N
~21 N
~24 N
~26 N
222
Fig. 14. SEM images of the wear pattern of: (a) the as-received substrate after a sliding distance of 5 m, (b) the sandblasted substrate after a sliding distance of 5 m, (c) the as-received
substrate after a sliding distance of 200 m, and (d) the sandblasted substrate after a sliding distance of 200 m.
223
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